CA1208208A - Sulfurized olefin-containing compositions - Google Patents

Abstract

SULFURIZED OLEFIN-CONTAINING COMPOSITIONS

Abstract New compositions are described which are useful as additives for lubricants, especially for multipurpose industrial oils. The compositions of the invention comprise (A) at least one aliphatic olefinic compound and (B) the sulfurization product of at least one aliphatic, arylali-phatic or alicyclic olefinic hydrocarbon containing from about 3-30 carbon atoms wherein the weight ratio of A to B
is no greater than 1:1.

Description

~LZ~'~320~

~UI.1~URIZ~D' ~L~F'IN`-CONT~'INING' t~MPO'~ NS
-- . . .
B'ACgG~ND' ~F' i~ 'INVENq~It)N

This in~ention relates to compositions useful as additives for lubricants, and, more particularly, for addi-tives useful in multipurpose industrial oils for use ingear, hydraulic and other specialt~ applications. In its broadest sense, the ~nvention relates to sulfuriæed olefin-containing compositions and lubricants and concentrates containing such composit~ons.
It is well known that the high pressure which occurs in certain types of gears and bearings may cause rupture of lubricant films with consequent damage to the machinery~ Because of the se~ere conditions under which they are used, industrial and gear lubricants ordinarily 15 must contain additives whtch maximi2e their capability of func~ioning under extreme pressure conditions. It has been suggested that certain compounds of metal-reactive elements, such as compounds of chlorine, sulfur, phosphorus and lead impart extreme pressure properties to various lubricants.
20 Among the various compositions kno~n to ser~e this purpose are various phosphorus- and sulfur-containing compositions, chiefly salts and esters of dialkylphosphoxodithioic acids, and sulfurization products of various aliphatic olefinic compounds. These two type~ of compositlons ha~e been used 25 in combination in lubr~cants of this type, and they serve to increase the e~ecti~eness of the lubricant under conditi~
of extreme pressure. 'r~' ~2~1208

- 2 -Many of the known sulfurization products of olefinic compounds contain substantial amounts of active sulfur. The presence of active sulfur in a lubricant often has deleterious side effects such as staining of copper parts, increased wear on the metal components being lu-bricated, and a decrease in extreme pressure properties with the passage of time.
Various compositions prepared by the sulfuriza-tion of olefins have been described in the prior art as 10 being useful in lubricant compositions. For example, U.S.
Patent 4,191,659 describes the preparation of sulfurized olefinic compositions by the catalytic reaction of sulfur and hydrogen sulfide with olefinic compounds containing from

3 to 30 carbon atomæ. Such compounds are reported ~o be 15 useful in lubricating compositions, particularly those prepared for use as industrial gear lubriaants.
~UMM~ F TEE INVEN~ION

~ composition is described which comprises (A? at least one aliphatic ole~inie compound and (B) the sulfur~-zation product of at least one aliphatic, arylaliphatic or alicyclic olefinic hydrocaxbon containing from about 3-3a carbon atoms wherein the weight ratio of A to B is no 25 greater than 1:1. Such compositions are useful as lubricant additive comFositions, and more particularly, as additive compositions in industrial and gear lubricants. The com-positions when added to lubricants pxo~ide longer lasting extreme pressure properties and anti-wear capability and 30 ~educe staining o~ copper part~.
Component A in the compositions of the invention is at least one aliphatic olefinic compound which ~enerally will contain at least about 8 carbon atoms and preferably between about 8 and 3a carbon atoms. The aliphatic olefinic 35 compound useful as componen~ ~ in the compositions of the invention ma~ be an ole~n~c ~ydroca~bon such as l-octene, 1-decene, l-tetradecene, l-octadecene, 1-eicosene, etc.
Aliphatic olefinic compounds containing internal double ~L2~ !3208 bonds also are useful as component ~, and examples of such olefins include 2-decene t 5-decene, 9-octadecene, etc. The a-olefins are preferred, especially those containing from 12 to 20 carbon atoms. Mixtures of these olefins are available commercially, and such mixtures are contemplated for use in this invention.
Component A also may be a fatty acid, a fatty acid ester, or mixtures thereof. The term "fatty acid" as used herein refers to acids which may be obtained by hydrolysis 10 of naturally occurring vegetable or animal fats or oils.
These fatty acids usually contain from 16 to 20 carbon atoms and are mixtures of saturated and unsaturated fatty acids.
The unsaturated fatty acids generally contained in ~he naturally occurring vegetable or animal fats and oils ma~
15 contain one or more double bonds and such acids include palmi-toleic acid, oleic acid, linoleic acid, linolenic acid, petroselenic acid, erucic acid, gadoleic acid, vaccenic acid, ricinoleic acid and minor amounts of compounds con-taining more than 20 carbon atoms such as behenic acid~
The unsaturated fatty acids useful as component A
may compri~e mixtures of acids such as those ob~ained from tall oil or by the hydrolysis of peanut oll, soybean oil, cottonseed oil, sunflower seed oil, or wheat germ oi~. Tall oil is a mixture of rosin acids, mainly abietic acid, and 25 unsaturated fatty acids, mainly oleic and linoleic acids.
Tall oil is a by-product of the sulfate process for the manufacture of wood pulp.
The most preferred aliphattc olefinic compounds useful as component A in the compositions ~f the invention 30 are fatty acid esters which contain olefinic unsaturation in the fatty acid moiety. Of these types, the most particu-larl~ preferred are the ~a~ty Qils, that i~, naturally occurring esters of gl~cerol with the fatty acids described above, and synthetic esters of similar structure. Examples 35 o~ naturall~ occurrl~g fats and o~s containlng unsaturation include animal fats such as neat's-foot oil, lard oil, depot fat, bee~ tallo~, etc. Examples of naturally occurrin~
vegetable oils use~ul as component A ~nclude cottonseed oil, ~2(~8Z08 corn oil, poppy-seed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat germ oil.
The fatty acid esters which are useful as com-ponent A in the invention also may be prepared from alipha-tic olefinic acids of the type described above such as oleicacid, linoleic acid, linolenic acid, and behenic acid by reaction with alcohols and polyols. Examples of aliphatic alcohols which may be reacted with the above-identified acids include monohydric alcohols such as methanol, ethanol, 10 n-propanol, isopropanol, the butanols, etc.; and polyhydric alcohols including e~hylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, glycerol, etc~
Component B in the compositions of this lnvention is a sulfurization product of at least one alipha~ic, aryl-15 aliphatic, or alicyclic olefinic compound containing about3-30 carbon atoms. The olefinic compounds which ma~ be sulfurized to form component B are diverse in nature. They contain at least one olefinic double bond, which is defined aæ a non-aromatic dauble bond; that is, one connecting two 20 aliphatic carbon atoms. In its broadest sense, the olefin may be defined b~ the ~ormula RlR2C=CR3R4, wherein each of Rl, R2, R3 and R4 is hydrogen or an organic radical. In general, the R values in the above formula which are not hydrogen may be sa~isfied by such groups as -R5j -C(R5)3, 25 -COOR5, -CON(R5) 2 ~ -COON(Rs~ 4 -COOM, -CN, -C-Rs, -X or -YRs, whereîn:
Ea~h Rs is independently hydrogen, alkyl, alkenyl, aryl, alkylaryl, substituted alkyl or substituted alkenyl, with the pro~iso that any two R 5 groups can be alkylene or 30 substituted alkylene whereby a ring of up to about 12 carbon atoms is formed;
M is one equivalent of a metal cation tpre~erably Group I or II, e.g., sodium~ potassium, barium, calcium~; -X is halogen (e.g., chloxo, bromo, or iodo);
~ is ox~gen ox divalent sulfur.

)!3Z08 Any two of Rl, R2, R3, and R4 may also together form an alkylene or substituted alkylene group; i.e., the olefinic compound may be alicyclic.
The nature of the substituents in the substituted moieties described above is not normally a critical aspect of the invention and any such substituent is useful so long as it is or can be made compatible with lubricating environ-ments and does not interfere under the contemplated reaction conditions. Thus, substituted compounds which are so un-stable as to deleteriously decompose under the reactionconditions employed are not contemplated. However, certain substituents such as keto or aldehydo can desirably undergo sulfurization. The selection of suitable substituents is within the skill of the art or may be established through routine testing Typical of such substituents include any of the above-listed moieties as well as hydroxy, carboxy, carbalkoxy, amidine, amino, sulfonyl, sulfinyl, sulfonate, nitro, phosphate, phosphite, alkali metal mercapto and the like.
The olefinic compound i5 usually one in which each R group which is not hydrogen is independently alkyl or alkenyl, or (less often~ a corresponding substituted radi-cal. Monoolefinic and diolefinic compounds, particularly the former, are preferred~ and especially terminal mono-25 olefinic hydrocarbons; that is, those compounds in which R3 and R4 are hydrogen and R~ and R2 are alkyl (that is, the olefin is aliphatic~. Olefinic compounds having about 3-30 and especially about 3-20 carbon atoms are particularly desirable.
The ole~inic compound also can be an arylaliphatic compound, particularly wherein the aryl group is a phenyl or substituted phenyl group. Specific examples include sty-rene, ~-methyl styrene, vinyl toluene, 4-ethyl vinyl benzene, e~c~
Propylene, isobutene and thetr dimers, trimers and tetramers, and mixtures thereof are especially pre~erred olefinic compounds. Of these compounds, isobutene and ~2~ZO~

diisobutene are particularly desirable because of their availability and the particularly high sulfur-containing compositions which can be prepared therefrom.
The sulfurizing reagent used for the preparation 5 of component B may be, for example, sulfur, a sulfur halide such as sulfur monochloride or sulfur dichloride, a mixture of hydrogen sulfide and sulfur or sulfur dioxida, or the like. Sulfur-hydrogen sulfide mixtures are often preferred and are frequently referred to hereinafter; however, it will 10 be understo~d that other sulfurization agents may/ when appropriate, be substituted therefor.
The amounts of sulfur and hydrogen sulfide per mole of olefinic compound are, respectively, usually about 0.3-3.0 gram-atoms and about 0.1-1.5 moles. The preferred 15 ranges are about 0.5-2.0 gram-atoms and about 0.4-1.25 moles respectively, and the most desirable ranges are about 0.8-1.8 gram-atoms and about 0.4-0.8 mole respecti~ely.
The temperature ra~ge in which the sul~urization reaction is carried out is generally about 50-350C, The 20 pre~erred range is about 100-2aOC., with about 125-180C.
being especially suitable. The reaction is often preferably conductad under superatmospheric pressure; this may be and usually is autogenous pressure (i.e., the pressure which naturally develops during the course o~ the reactlon~ but 25 may also be externally applied pressure. The exact pressure deveioped durin~ the reaction i~ dependent upon such factors as the design and operation of the system, the reaction temperature, and the vapar pressure of the reactants and products and it may vary dur~ng the course of the reaction.
It is frequently advantageous to incorporate materials useful as sulfurization catalysts in the reaction mixture. These materials may be acidic, bas~c or neutral, but are preferably basic materials, especially nitrogen bases including ammonia and amines The amount of catalyst 35 used is generally about 0 05 2.0~ o~ the weight of the Glefinic compound. In the case of the preferred ammonia and amine catalysts, about Q.0005-0.5 mole per mole of olefin is ~208208 preferred, and about 0.001-0.1 mole is especially desirable.
Following the preparation of the sulfurized mixture, it is preferred to remove substantially all low boiling materials, typically by ventiny the reaction vessel or by distillation at atmospheric pressure, vacuum dis-tillation or stripping, or passage of an inert gas such as nitrogen through the mlxture at a suitable temperature and pressure.
A further optional step in the preparation of component B is the treatment of the sulfurized product, obtained as described hereinabove, to reduce active sulfur.
An illustrative method is treatment with an alkali metal sulfide as described in U.S. Patent 3,498,915. Other optional treatments may be employed to remove insoluble by-products and improve such qualities as the odor, color andstaining characteristics of the sulfurized compositions.
U.S. Patent 4,119,549 discloses suitable sulfuriza-tion products useful as component B. Several specific sulfurized compositions are described in the working examples thereof. The following example illustrates the preparation of one such composition.
Example A
Sulfur (629 parts, 19.6 moles) is charged to a jacketed high-pressure reactor which is fitted with an agitator and internal cooling coils. Refrigerated brine is circulated through the coils to cool the reactor prior to the introduction of the gaseous reactants. After sealing the reactor, evacuating to about 6 torr and cooling, 1100 parts (19.6 moles) of isobutene, 334 parts (9.8 moles) of hydrogen sulfide and 7 parts of n-butylamine are charged to the reactor. The reactor is heated using steam in the external jacket, to a temperature of about 171C. over about 1.5 hours. A maximum pressure oE 720 psig. is reached at about 138C. during this heat-up. Prior to reaching the peak reaction temperature, the pressure starts to decrease and continues to decrease steadily as the gaseous reactants B%08 are consumed. ~fter about 4.75 hours at about 171C., theunreacted hydrogen sulfide and isobutene are vented to a recovery system. Ater the pressure in the reactor has decreased to atmospheric, the sulfurized mixture is re-covered as a liquid.
As mentioned above, the sulfurizing agent may besulfur, and the reaction is effected by heating the olefinic compound with sulfur at a temperature of from 100-250C., usually about 150 210C~ with efficient agitation and in an lO inert atmosphere (e.g., nitrogen). The weight ratio of olefin to sulfur may be as high as 15:1 and is generally between about 5:1 and 10:1.
It is frequently advantageous to add the sulfur portionwise to the olefin. While it is usually preferred 15 that the reaction mixture consist entirely of the olefin and sulfur, the reaction may be effected in the presence of an inert solvent such as alcohol, ether, ester, aliphatic hydrocarbon or halogenated aromatic hydrocarbon which is a liquid at the xeaction temperatures employed.
Following the reacti~n, insoluble by-products may be removed by filtrati~n, usually at an elevated te~perature ~about 80-120C.). The f~ltrate is the desired sulfurized product The compositionS of this invention typically con-25 tain components ~ and B in a ~eight ratio no grea~er thanl:l. Generall~, the weight ratio of component A to com-ponent B is from about 0.2:1 to about l:l, and more pre-ferably, from about 0 2:1 to about 0.5:1. The compositions of the invention may be prepared merely by blending the 30 ingredients, either undiluted or in substantially inert diluentsO The diluent, if any, may be the oil used as a lubricant base and may include other additives such a~ those described hereinafter.
The follo~ing examples are illustrative of the 35 compositions of thls ~nventi~n:

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As previously indicated, the compositions of this invention are useful as additi~es for lubricants, in which they function primarily as extreme pressure and anti-wear agents; the addition of the compositions of the invention also results in a reduction in staining of copper parts.
They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof. These lubricants include crankcase lubricating oils for spark-10 ignited and compression-ignitsd internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, sta-tionary power engines and turbines and the like. Automatic 15 transmission fluids, transaxle lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can al~o benefit from the incorporation therein of the compositions of the present invention.
However, the compositions are particularly useful in gear 20 lubricants and eQpecially industrial gear lubricants~
Natural oils in~lude liquid petroleum oils and solvent-treated or acid-treated mineral lubri~ating oils of the paraffinic, naphthenic and mixed paraffinic-naphtheni~
types. Oils of lubricating viscosity derived from coal or 25 shale are also useful base oil~. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins le.g., polybutylenes, polypropylenes, propylene-isobutylene co-polymers, chIorinated polybutylenes, poly(l-hexenes), poly-30 (l-octenes), poly(l-decenes), etc. and mixtures thereof];
alkylbenzenes le.g., dodecylbenzenes, tetxadecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.]; poly-phenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl 35 sulfides and the derivatives, analogs and homologs thereof and the like.

~L2~3208 Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc.
constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide t the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-10 ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, e~c.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters, or the Cl 3 OXO acid diester of 15 tetraethylene glycol.
Another suitable class of synthetic lubricatîng oils comprises the esters of dicarboxylic acids (e.gc, phthalic acid, succinic acid, alkyl suc¢inic acids and alkenyl succinic acids, maleic acid, azelaic acid, su-20 beric acid, sebacic acid, fumaric acid, adipic acid, lin-oleic acid dimer, malonic acid, alkyl malonic acids, al kenyl malonic acids, etc.) with a vaxiety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethyl-hexyl alcohol, ethylene glycol, diethylene glycol monoether, 25 propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, di-isodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic 30 acid dLmer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those made from Cs to Cl 2 monocarboxylic acids and polyols and 35 polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaexythritol~ etc.

3~

Silicon~based oils such as the polyalkyl-, poly-aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and si-licate oils comprise another useful class of synthetic lubricants [e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-silox-anes~ poly(methylphenyl)siloxanes, etc.]. Other synthetic lubricating oils include liquid esters of phosphorus-con-10 taining acids (e.g., tricresyl phosphate, trioctyl phos-phate, diethyl ester of decylpho~phonic acid, etc.), poly-meric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-15 inabove can be used in the lubricant compositions of thepresent invention. Unrefined oils are those obtained di rectly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained 20 directly from distillation or ester oil obtained directly from an esterification process and used without further trea~ment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or 25 more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction~ fil~ration, percolation, etc.
Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which 30 have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention 35 contain an amount of the composition of this invention sufficient to provide it with extreme pressure and anti~wear properties. Normally this amount will be about 0.01 to ~Z~82~8 about 10~, preferably about 0 01 to about 5% of the total weight of the lubricant. In lubricating oils operated under extremely adverse conditions, the reaction products of this invention may be present in amounts of up to about 20% by weight.
The invention also contemplates the use of other additives in combination with the compositions o this invention. Such additivex include, for example, detergents and dispersants of the ash-producing or ashless type, cor-10 rosion- and oxidation-inhibiting agents, pour point de-pressing agents, auxiliary extreme pressure agents, color stabilizers and anti-foam agents.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline 15 earth metals ~ith sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing 20 agent such as phosphoru~ trichloride, phosphorus hepta-sulfide, phosphorus pen~asulfide, phosphorus ~richloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-thioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, 25 strontium and barium.
The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. The commonly employed methods for preparing the basic salts involva heat-30 ing a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid 35 the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, ~LZ~Z. ~

thiophenol, sulfurized alkylphenol, and condensation pro-ducts of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, car~itol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol 10 promoter, and carbonating the mixture at an elevated tem~
perature such as 60-200C.
Ashless detergents and dispersant~ are so called despite the ~act that, depending on its constitution t the dispersant may upon combustion yield a non-volatile material 15 such as boric oxide or phosphorus pentoxide; howe~er, it does not ordinarily contain metal and therefore does not yield a metal-contaîning ash on combustion. Many types are known in the art, and any o them are suitable for u~e in the lubricants o~ this invention. The following are illus-20 trative:
(1) Reaction produc~s of carboxylic acids (orderivatives thereof) containing at least about 34 and pre-ferably at least about 54 carbon atoms with nikrogen-con-taining compounds ~uch as amine, organic hydroxy compounds 25 such as phenols and alcohols, and~or basic inorganic ma-terials. Examples of these "carhoxylic disper~ants" are described in British Patent 1, 306 ~ 529 and in many U.S.
patents including the following:
3 ~ 163 ~ 603 3 ~ 351 ~ 552 3 ~ 541,012 3~184~474 3~381~Q22 3~542t678 3~215~707 3~399~141 3~542~680 3~219~666 3~415~750 3~567~637 3l271,310 3~433~744 3~574~101 3~272~746 3~444~170 3~576~743 3~281~357 3~448~048 3~30~904 3~306~908 3~448 jO49 3,632r510 3~311~558 3~451~933 3~632~511 r ~21)~3:208 3,316rl77 3,454,607 3,697,428 3,340,281 3,467,66~ 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecu-lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be characteri~ed as "amine dispersants" and examples thereof are described for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains a~ least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially 15 polyalkylene polyamines), which may be characterized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative:
2,459,1123,44~,808 3,591,598 2,962,4423,448,047 3,600,372 2~ 2,984,5503,454,497 3,634~515 3,036,0033,459,661 3,649,229 3,166,5163,461,172 3,697,574 3,236,7703,493,520 3,725,277 3,355,2703,539,633 3,725,4 3,368,9723,558,743 3~726,88 3,413,3473,586,6~9 3,980,569

(4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, car-30 boxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:

3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522

(5) ~nterpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be characterized as "polymeric dispersants" and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 The above-noted patents disclose ashless dispersants.
Auxiliary extreme pressure agents and corrosion-and oxidation-inhibiting agents are exemplified by chlo-rinated aliphatic hydrocarbons such as chlorinated wax;
aromatic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) disulfide, and sulfurized alkylphenol;
phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate;
phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, di-heptyl phosphite, dicyclohexyl phosphite, pentylphenylphosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phospite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)~substituted phenyl phosphite, diisobutyl-substituted 8Z~8 phenyl phosphite; metal thiocarbamates, such as zinc di-octyldithiocarbamate, and barium heptylphenyl dithiocar-bamate; Group II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodi-thioate, barium di(heptylphenyl)phosphorodithioate,cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phos-phorus pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl alcohol.
Tha compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concen-15 trates usually contain about 20-90~ by weight of the com-position of this invention such as the compositions of Examples 1-6 and may contain, in addition, one or more other additives known in the art or described hereinabove.
Illustrative lubricants of this invention comprise 20 principally mineral oil (e.g., SAE lOW-40 for an internal combustion engine lubricant and SAE 75W-90 for a gear lubricant~ in combination with about 0.5-5.0~ by weight or more of the composition of the invention such as Examples 1-

6 and with other known lubricant additives. The following 25 specific examples in Table II illustrate lubricating com-positions according to the invention. Unless otherwise indicated, all amounts listed, except those for mineral oil, are exclusive of oil present as diluent.

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Claims (17)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition comprising (A) at least one ali-phatic olefinic compound containing at least about 8 carbon atoms, and (B) the sulfurization product o at least one aliphatic, arylaliphatic or alicyclic olefinic hydrocarbon containing from about 3-30 carbon atoms wherein the weight ratio of A to B is no greater than 1:1.

2. A composition according to Claim 1 wherein component A is at least one .alpha.-olefin.

3. A composition according to Claim 2 wherein component A is at least one .alpha.-olefin containing from about 12 to 20 carbon atoms.

4. A composition according to Claim 1 wherein component A is at least one fatty acid ester containing olefinic unsaturation in the acid moiety.

5. A composition according to Claim 4 wherein component A is at least one fatty oil.

6. A composition according to Claim 5 wherein component A is soybean oil.

7. A composition according to Claim 1 wherein component A is at least one fatty acid.

8. A composition according to Claim 7 wherein the fatty acid is tall oil acid.

9. A composition according to Claim 1 wherein component B is a sulfurization product of at least one aliphatic olefinic compound containing from about 3 to 20 carbon atoms.

10. A composition according to Claim 1 wherein component B is a sulfurization product of at least one of propylene, isobutene and dimers, trimers and tetramers thereof.

11. A composition according to Claim 9 wherein component B is prepared by reacting the olefinic compound with a sulfur halide or a mixture of sulfur and hydrogen sulfide.

12. A composition according to Claim 10 wherein component B is prepared by reacting isobutene with a mix-ture of sulfur and hydrogen sulfide.

13. A composition according to Claim 10 wherein component B is prepared by reacting isobutene with a sulfur halide.

14. A composition according to Claim 13 wherein the sulfur halid is sulfur monochloride.

15. A composition according to Claim 1 wherein the weight ratio of component A to component B is from about 0.2:1 to 0.5:1.

16. An additive concentrate comprising a substan-tially inert, normally liquid organic diluent and from about 20 to 90 percent by weight of a composition accord-ing to any one of Claims 1, 5 or 9.

17. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of a com-position according to any one of Claims 1, 5 or 9.